Process of cracking and oxidizing oils



Patented Jan- L 1929.

UNITED STATES cam-Eran anus,

PATENT OFFICE.

OI IONTGLAIB, NEW JERSEY, ASSIGNOR'TO ELLIS-FOSTER Pm, A. CORPORATION OFNEW JERSEY.

promise or enactment]: oxmrzmo 611s.

'80 Drawing. original application filed January 3, 1922, Serial No.526,655. Divided and this application 1 I filed. Octoberlt, 1924. SerialN6. 743,453.-

This invention relates to a method of pro-- ducing' gasoline and otherhydrocarbons from petroleum and also various products of oxidation whichare derived from the union of -5 oxygen with the products of crackingheavier oils. The invention is concerned not only with the productionofgasoline by cracking an oil but also the oxidation of some part of theproducts of cracking particularly the unsaturated components as forexample the olefins or other unsaturated substances produced by, thecracking of heavy oils'such as petroleum oil, asphalt, gilsonite, fatsand greases and the like. While the invention has many modifications-andthe sources of raw'material are varied the process will be described bymeans of the use of oil gas as an illustrative procedure. Whilethetreatment of cracked material will be more specifically set forthbelow, the processes of oxidation therein disclosed are equallyapplicablie to the treatment of uncracked petroleum 01 s.

For this purpose heavy petroleum oil, first purified by means of adesulphurizing agent, 7 may be dropped into a. heated pan and allowed tobecome volatilized, the gases and vapors being passed through anelongated strongly. heated retort or cracking tube so as'to yield a highpercentage of lighter hydrocarbons= including unsaturated bodies. Insome cases these may constitute a very substantial portion of the fixedgases or very. light constituents as for example twenty-five to fortyper cent. These gases and vapors may be carried thi'ough a condensingapparatus, hydraulic seal and the like by means of, which the heaviercomponents, tars, etc, are removed. If desired the products may bepassed through scrubbers or compressors to remove the heavierconstituents which. are not so easily condensed in the previous-stage ofcondensation. Thus by these condensation steps light oils are obtainedwhich'may be rectified to yield gasoline or motor spirit. In one form ofthe invention the residual gases and vapors may be then subjected to apurification process to remove sulphur compounds or to remove any otherundesirable constituents in case these be present. Such gases and vaporscontain a substantial percentage of propylene and butylene and analogousolefinsand are well adapted for catalytic oxidation treatment with airand contacting with catalytic material. The gases and vapors thereforeare mixed with air and are introduced into a catalytic chamber where themixture is brought into contact with .a catalyzer such as a spiral ofcopper gauze or brass, iron or any other suitable catalytic material inthe form of the metal as for example pieces of wire gauze or frag mentsofthe metal. As a substantial evolution of heat occurs on oxidation theuse of a metal catalyzer for oxidizing compounds having the high heat ofcombustion characteristic of petroleum hydrocarbons affords a desirablemeans of conducting away excess heat. Since the regulation oftemperature, especially prevention of too high a temperacom I tureisquite important in the oxidation of petroleum the application of afrag'mental catalytic mass of metal or material havingthe heatconductivity, of metal is a'de'sirable temperature control. i Compoundssuch means of assisting in the important factor of is also possible tosupport the catalyzer on any other suitable carrier ifdesired. Forexample in small apparatus where theheat evolution is not so important afactor pumice may be used. Such substantially non-conducting carriersmay also be used in larger apparatus if suitable provision is made toabsorb any excess heat. For example a mixture of the gas thus obv tainedby cracking and containing a substantial percentage of olefins is mixedwith air in quantity somewhat in excess of that required to: oxidize theolefins to form for example, ketones and the mixture is passed-over a.spiral of copper gauze which is maintained at a temperature just belowa. low red heat. Anincipient or low redheat is about 500 to 525C. and Ipreferably do not permit the temperature to exceed525 C. Preferably a ascopper or chromium oxide, iron vanadate, silver chromate, molyb-- 'blackheat'is employed just below a low red vantage. As for example at apressure of 10 atmospheres a temperature of 200 to 300 C. may be used insome cases. The products issuing from the catalytic chamber may bedirectly passed into water or may be first passed through a condenserand any condensable material first removed, thus any steam formed by theoxidation or present in the incoming air may becondensed and carry withit various Water soluble products. Hydrocarbons also may condense andseparate above the water layer. Steam may be used to control thevtemperature in the catalytic mass or when no catalyzer is employed as ameans of preventingtoo violent reaction or explosion. The steam mayhowever be omitted. In any event any water which has formed by the(0111-- bustion may be collected to some extent at least by suitablecondensation. Or the products from the catalytic or oxidation chambermay pass into. water and the water soluble may be introduced which willprovide the substances thus collected. The residual gases may be passedinto an 011 scrubber or silica gel 1f deslred. Or water washing may be asec- 0nd stage of operation or omitted entirely,

oil scrubbing or silica'gel being used. Activated carbonimay be used asan absorbing agent.

In the aqueous solution from the oxidation will be found the alcohols,ketones, aldehydes, acids, quinones and other water soluble products ofoxidation which may be formed. These will vary with different conditionsof operation and nature of the raw material.

In thejpresent invention, in one phase at least, it is an object toutilize kerosene hydrocarbons the major portion of which boil sub,-stantially below 250 or 300 C. Kerosene is readily vaporized and issuitable for this,

phase of the invention. Anypetroleum hydrocarbon which isreadilyvaporizable and boils below 300 C. may be used in carrying out thisphase of the invention.

In employin kerosene, first purified by. means of a desu phurizingagent, it may for example be passed through a heated tube'or crackedunder pressure to produce gasoline and gases. The gasoline is suitablycollected and the gases employed forthe oxidation.

- Or the gasoline may be vaporized, admixed .with air and submitted tooxidation. In the first procedure the kerosene may be passed through aheated tube at a temperature of 500 to 700 C. The products may be thenpassed through a condenser, the light portions submitted to catalyticoxidation or the entiremixture of cracked products maybe passed throughthe catalytic mass in admixture with air or an oxygen-containing gas.All the air may be added at once or if. desired the air may be added atintervals within the catalytic mass. The air may be preheated by passingit about the catalytic chamber or the receptacle in whichoxidation is inprogress..

The regeneration of the heat developed in the operation is desirable andit is not necessary in all cases to utilize the heat for the purpose ofpreheating the incoming air or the incoming mixture of air andhydrocar-, bon vapors or gases. The heat may be utilized in other ways.The temperature maybe kept below a low red heat or incipient red heat,that is below approximately 500 C. through the introduction of a lesserquantity of air than that which would serve to oxidize the entire body.of hydrocarbons to alcohols, aldehydes, ketones, organic acids orwhatever particular product was desired. The use of a quantity of airsuiiicient only to oxidize a minor portion of the hydrocarbons to theorganic derivative desired is a feature of the present invention. If forexample the gases and vapors are rich in olefins containing say 'ten totwenty per cent or more a quantity of air or oxygen on otheroxygen-containing gas portion is at least fifty per cent of the totalproducts calculated as hydrocarbons and organic bodies containingoxygen. This does not include the carbon monoxide, carbon dioxide, wateretc.

' In the case of vapors or gases which are free-from olefins as forexample still gases, the olefins of-which have been scrubbed in somemanner to remove the olefins, thesame ,proportions hold with respect tothe amount of oxygen to be employed. The oxidation to carried out is sothat an abundance of hydrocarbon is present in the exit gases andvapors.

The oxidation of kerosene as referred to above carried out in thismanner employing a catalyzer of vanadium oxide and a temperature of 300to400 C. yields aldehydcs and fatty acids. A small amount of formal-.dehyde is produced and higher aldehydes.

Thetreatmentof the aqueous solution containmg aldehydes and acids ispreferably as follows: If the aldehyde is desired in the free state thesolution is rendered neutral with caustic soda and distilled with steam.The

aldehyde is carried over and the aqueous solution becomes practicallyodorless. The higher aldehydes maybe employed in warious ways forexample they may be made to'react with caustic soda to form a esinoussub stance. In'one case a resin 0 this sort was produced from keroseneand was obtained in the form of a light brown powder' which could bemelted to a resinous substance. The aldehydes also apparently polymerizeduring the oxidizing operation to some extent.

The neutral solution conitaining the salts of organic acid may berendered very slightly acid with sulphuric or phosphoric acid and theorganic acids distilled. In the case of the kerosene treatmentreferredto above a mixture of organic acids was obtained which werevolatile with steam. These evidently consisted largely of propionic,butyric acids etc. On blowing a strong current of steam through theaqueous solution the distillate was acid.

Acids were separated readily in this way or by distillationwithout-steam. Hydroxy or dibasic acid,'if formed, may be used-for suchF operations as bleaching 1n substitution for oxalic acid etc. or mayfind uses in food prod'- ages, syrups etc.

-u.cts where an organic acid is desired to give a degree of aciditycomparable with citricacid as for example in'making various bever- 'Insome cases the catalyzer may be omitted the mixture of oil vapor and airwith or without steam being passed through a heated tube the walls ofwhich are substantially without catalytic efiect. The temperature ismaintained below a red heat which avoids igniting conditions besidesprevents violent combus tion or explosion; Temperatures of a red heat ora bright red heat such as have heretofore been recommended are highlydestruc-' tive to the products of oxidation and in the present inventionare not used it beingnecessary to maintain the temperature below a lowred heat. If the gaseous mixture is heated to a point slightly below theignition temperature: valuable oxidation reactions progress even thougha catalytic substance is not pres ent. j I In one phase of the inventionthe oxidation of the pr'opyl group of immediate higher hydrocarbongroups such as butyl, a-myl and the like is especially considered. Whenpetroleum oils are subjected-to heat decomposi-' tion a substantialproportion of propyl groups are renderedavailable by such crackingtreatment. It'was commonly supposed unusual stability and thereforeis-found in the that the breakdown yielded ethylene,

methane and the like in very large degree but it appears that the propylgroup is, one of products of-cracking in the form of propylene, propaneor hydrocarbons readily yield ing the propyl group to oxidizing action.

.The oxidation may go and does go to a further ,tofore quite costly.

stage that of producing propionic acid, butyric acid and the like sothat the invention is also concerned with producing fatty acids higherin the series than acetic acid but more especially the lower fatty acidsabove acetic which are readily volatile or easily volatilizedwithfsteam; These fatty acids are of value inproducing flavoringcompounds, like and from. petroleum oil by means of the processdescribed above esterified products have 'been obtained which havedesirable fruity odors.

For example by neutralizing the acid water artificial fruit essences andthe cerned in one aspect, with the cracking of petroleum oils toliberate propyl groups or immediate higher homologues in a veryavailable form for air oxidation and converting such availablegroupsinto propionic and higher fatty acids and other bodies mentioned.

The present invention thus opens the way of the petroleum refiner toproducefatty acids from petroleum which on esterification yield estershaving promis ipg applications as artificial fruit flavors, in perfumesand in other fields. heretofore remote from the petroleum industry.

amyl alcohols are prepared from still gases;

such methods having as the basis, the use of sulphuric acid, asanabsorbing agent. The petroleum refiner thus may produce alcoholson'the one hand and fatty acids on the Methods are already known bymeans of which, alcohols :e. g. ethyl, propyl, butyl,

other-and by suitable combination. prepare at v a relatively low cost avariety of esters ,here- The absorption method involving the use ofsulphurie acid to which I have referred does'not form any part of thepresent invention. 1

What I claim is:- 1. Inthe'process including oxidation of kerosene oilby-treatmentwith an oxygen- .containing gas at a'temperature below a redheat under conditions to produce substantial oxidation and collectionofthe oxidizedproducts, the step of using ail-amount of oxygen suflicientto oxidize my a minor portion of,

the hydrocarbons 0 said kerosene oil. I 2. In the process of oxidizingpetroleum oil by treatment with an oxygen-containing gasat a temperaturebelow a red heat under conditions toproduce substantial oxidation, the

- step of using an amount of oxygen suflicienttooxidize only a minorportion of the hydrocarbons of said petroleum oil.

v .3. In the process of oxidizing a desulphurized petroleum oilwith anoxygen-containing gas at a temperature below a red heat under conditionsto produce substantal oxidation, the step ofuslng anzamount of oxygensufficient to oxidize only a minor portion of the hydrocarbons of saiddesulphurized petroleum oil.- P

4. In the process of oxidizing a desulphurized kerosene oil bytreatment-with an oxygen-containing gas at a temperature below a redheat under conditions to produce substantlal oxidation, the step ofusing an amount of oxygen sufiicient to oxidize only a catalytic massunder conditions to produce substantial oxidation followed by collectingthe aldehyde produced by oxidation, the step of oxygen suflicient tooxidize or ly a minor portion of the hydrocarbon contained in saiderosene vapors. Y

7. In the process of making an aldehyde by. treating petroleum vaporsand air at a temperature elow a red heat in the. presence of a. catalystunder conditions to' produce substantial oxidation followed bycollecting the aldehyde produced by oxidation, the step of 'uslng anamount of oxygensuflicient td oxidize only a minor portion of thehydrocarbons contained in the petroleum vapors.

8.- In the process of making aldehydes and acids by treating vapors fromdesulphurized petroleum and air in the presence of a catalyst at atemperature below a red heat under cond tions to produce substantialoxidation.

followed by collecting the aldehydes and acids produced by oxidation,the step of of using 1n the treatment process, an amount using an amountof oxygen sufficient to oxidize only aminor portion of the hydrocarbonscontained in the petroleum vapors.

9. In the process of making aldehydes and aldeh de polymers b treatingvapors from petro eum boiling be ow 300 C. and air in the presence of acatalyst at a temperature below a low red-heat under conditions toproduce substantial oxidation, the step of using an amount of oxygensufiicient to oxidize only a minor'portion of. the hydrocarbons of suchpetroleum vapors, and then collecting thealdehyde produced by oxidation.10. In the process of oxidizing a petroleum oil boiling below 300 C. bytreatment 7" with oxygen at a temperature below a low red heat underconditions to produce substantial oxidation, the step of using an amountof oxygen sufficient to oxidize only a minor portion of thehydrocarbonsof said 7 petroleum oil, and then collecting the oxidized products; Y

, 11-.'In the process of oxidizing a petroleum oil boiling below 300 C.with air at a temperature below a low red heat under eon-" 8 ditions toproduce substantial oxidation fol= lowed by collecting the oxidizedproducts,

the step of using an amount of oxygen sufficient to oxldize only a mlnorportion of the hydrocarbons contained in said petroleum 35 *oilw 12.,--.In the process of oxidizing a petro leum oil by treatment with anoxygen-containing gas at a temperatur'e between 400 and 500 C. underconditions to produce substan-- tiaI oxidation, the step of using anamount of oxygen suflieient to oxidize only a minor portion of thehydrocarbons of the petro leum oil.

oil by treatment with an oxygen-containing gas at a temperature below ared heat under conditions to produce substantial oxidation, wlnle \v''ithdrawing heat from the oxidation zone, the step of using an amount ofoxygen 10o suflicient to oxidize only a, minor portion ofthe-hydrocarbons of said petroleum oil.

14; In the process of oxidizing petroleum oil by treatment withanoxygen-containing gas at a temperature below a red heat under conditionsto produce substantial oxidation, the step of using anamount of'oxygensufficient to oxidize only-a minor portion of the hydrocarbons of thepetroleum oil whereby at least 50% of hydrocarbons are left int-heend-productscalculated as lnvdrocarbons and organic bodies containingoxygen, exclusive cof the carbon monoxide, carbon dioxide, and

water present in the end products.

15. In the process including oxidation of petroleumoil by treatment withan. oxygencontainin gas at a temperature below a red heat an atsuper-atmospheric pressure under conditions to produce substantial oxi-vdation, the step of using an amount of oxygen sufiicient to oxidize onlya minor portion of said petroleum o1].

oARLETo ELLIS;

13. In the process of oxidizing petroleum 95

